Allyl halide-monoolefin condensation product

ABSTRACT

A distillate fuel having improved cold flow containing a low molecular weight product obtained on reacting an allyl halide and a C10 to C20 olefin using an aluminum halide as a catalyst, the molar ratio of allyl halide to olefin being from 5:1 to 1:10. This reaction product is characterized by having a molecular weight of from about 550 to about 1,200. A suitable allyl halide is allyl chloride; suitable olefins are decene, dodecene, tetradecene, heptadecene, octadecene and the like.

Unite States Patent 1191 Messina Aug. 27, 1974 [5 ALLYL HALIDE-MONOOLEFIN 3,290,397 12/1966 Rust 260/651 CONDENSATION PRODUCT 3,342,883 9/1967 Liston 260/658 C [75] Inventor: Steve J. Messina, St. Clair Shores, Pn-mwy Examiner Leon Zitver Mlch' Assistant Examiner-Joseph A. Boska [73] Assignee: Ethyl Corporation, Richmond, Va. i am Agent, or Firm-D0na1d lohnsom-Roberl 22 Filed: Aug. 21, 1967 [21] Appl. No.: 661,792 [57] ABSTRACT A distillate fuel having improved cold flow containing [52] US. Cl. 260/654 R, 44/79 a 10W molcular weight Product Obtained reacting 51 1m. (:1. C07C 21/02 an allylhalide and a Cw 0 Olefin using an alumi- [58] Field of Search... 260/654, 658 C, 658, 654 R, num halide as a catalyst, the molar ratio of allyl halide 2 0 54 5 54 H, 59 0 3 to olefin being from 5:1 to 1:10. This reaction product is characterized by having a molecular weight of from 5 References Cited about 550 to about 1,200. A suitable allyl halide is UNITED STATES PATENTS allyl chloride; suitable olefins are decene, dodecene, 2418 832 H H f d t 1 260/658 C tetradecene, heptadecene, octadecene and the like.

an or e a 3,002,033 9/1961 Feighner 260/658 3 Claims, N0 Drawings ALLYL HALIDE-MONOOLEFIN CONDENSATION PRODUCT BACKGROUND OF THE INVENTION Residual and distillate petroleum hydrocarbons are used as fuels in various applications. They are used as diesel fuels, jet fuels, home heating fuel, turbine fuels, rocket fuels, and in similar combustion systems. It is recognized that the fluidity of fuel oils in general is reduced as they are cooled. Additives which reduce the tendency of these fuels to become more viscous at low temperatures are available and are called pour point depressants. Another phenomenon which occurs when these fuels are cooled is that orifices and other narrow openings through which the fuel passes tend to become plugged. This occurs even when the fuel oil contains pour point depressants adequate to maintain proper viscosity at low temperatures. This latter characteristic of fuel oils, that is, their ability to flow through narrow orifices at low temperatures is referred to as cold flow.

In view of this need to overcome orifice plugging at low temperatures, additive which function as cold flow improvers in fuel oils are of substantial importance. The present invention comprises the discovery of an allyl halide/olefin reaction product which is effective as a cold flow improver in distillate fuels.

SUMMARY OF THE INVENTION DESCRIPTION OF PREFERRED EMBODIMENTS It is an object of this invention to provide a product from a process which comprises reacting an allyl halide with an olefin, the molar ratio of allyl halide to olefin being about 5:1 to about 1:10 using an aluminum halide catalyst. This product is characterized by having a molecular weight of from about 550 to about 1,200. It is a further object of this invention to provide a distillate fuel having improved cold flow properties containing a small quantity of the allyl halide/olefin product described above. Another object of this invention is to provide a method of improving the cold flow characteristics of the fuel oil by adding thereto a small quantity of the allyl halide/olefin reaction product. These and other objects of the invention will be made clear from the description and claims which follow.

An embodiment of this invention is the product obtained from the process which comprises reacting an allyl halide with an olefin, said olefin having from about 14 to about 18 carbon atoms in the presence of a catalytic quantity of an aluminum halide selected from aluminum bromide and aluminum chloride, the allyl halide/olefin molar ratio being from about 5:1 to about 1:10, said product being characterized by having a molecular weight of from about 550 to about 1,200.

A preferred product is obtained when the allyl halideolefin molar ratio is from about 1:3 to about 1:8. A most preferred product is obtained when the reactants used in the preferred product molar ratio are octadecene-l and allyl chloride and the catalyst is aluminum chloride.

Another embodiment of this invention is a fuel oil containing a cold flow improving quantity of said allyl halide/olefin product described above. A preferred embodiment of this invention is the fuel oil described above wherein the concentration of said allyl halide- /olefin product is from 0.001 to about 1.0 percent by weight. Another preferred embodiment is the fuel oil described above wherein the concentration of the allyl halide/olefin product is about 0.01 to about 0.5 percent by weight. The present invention concerns the discovery that an allyl halide and an olefin can be reacted in the presence of an aluminum halide catalyst to produce an oil soluble product having a molecular weight of from about 550 to 1,200. The exact mechanism by which the reaction proceeds and the exact identity of the product are not known. The product may be considered to be a copolymer of allyl halide and olefin, but this hasnot been confirmed. This reaction will proceed with allyl halide to olefin molar ratios of 5: 1 to 1:10. The product which is of more particular interest in this invention is one in which the molar ratio of allyl halide to olefin is from about 1:3 to about 1:8. The reason for preferring this latter molar ratio will be explained below when discussing the cold flow results obtained. In the examples below the process for preparing the product is set out in detail.

Monoolefins having from 12 to about 24 carbon atoms are useful in carrying out the reaction. Monoolefins having from about 14 to about 18 carbon atoms are preferred. Useful monoolefins include terminal olefins such as nonadecene-l isobutylene tetramer, propylene hexamer, eicosene-l, dodecene-l, and the like, as well as internal olefins such as octadecene-2, heptadecene- 4, dodecen'e-3, and the like. Mixtures of olefins may be used. The most preferred monoolefins are octadecenel and octadecene-2.

Commercial olefin mixtures comprising monoolefins primarily are also useful. These commercial olefin mixtures are generally mixtures of a series of homologues having from 12 to about 20 carbon atoms. Thus, useful mixtures may contain dodecenes, tetradecenes, heptadecenes, octadecenes, nonadecenes, and the like in varying proportions. Particularly useful mixtures are those in which the C monoolefin predominates. By predominates I mean that the octadecenes make up at least about 40 percent by weight of the olefin mixture. Examples of these useful olefin mixtures are (a) 40 percent octadecenes, 60 percent C C C and C olefin mixture; (b) 50 percent octadecenes, 50 percent C C C C olefin mixtures; (c) 60 percent octadecene, 40 percent C C olefin mixture; ((1) percent octadecenes, 10 percent tetradecenes, 20 percent hexadecenes, and the like. These commercial mixtures are prepared in many ways. Generally, they are obtained by polymerizing low molecular weight olefins via the Ziegler catalyst route and by catalytically dehydrogenating suitable paraffins.

The allyl halide which is used to prepare the product of this process is suitably selected from allyl chloride, allyl bromide, and allyl iodide. Allyl chloride and allyl bromide are the preferred allyl reactants.

The process described above is catalyzed by an aluminum halide. Aluminum chloride and aluminum bromide are both useful as catalysts. The catalystic quantity of aluminum halide used may be varied. Generally, an amount from about 0.5 percent to about 5.0 percent by weight based on the total weight of reactants used, is useful; catalyst quantities of about 1 percent to about 3 percent by weight are especially useful. Thus, for example, if 80 parts of an olefin and 20 parts of an ally] chloride were to be reacted, 0.5 to about 5.0 parts by weight of an aluminum halide would be added as the catalyst.

The aluminum halide may be added to the reactants as a solid or as a solution. Addition of the aluminum halide in solution is preferred. Any aluminum halide solvent which will not adversely affect the reaction, may be used. Solvents which are particularly useful are alkyl halides having from two to about five carbon atoms. Examples of such solvents are ethyl chloride, 2-chloropentane, sec-butyl chloride, and the like. Especially preferred solvents are isopropyl chloride and npropyl chloride. Generally, a saturatedsolution of the aluminum halide in one of the alkyl halides is used.

Where a solvent is used for the aluminum halide, it is substantially removed from the reaction product after the reaction is completed.

The temperature at which the reaction between allyl halide and olefin is carried out is not critical. Temperatures from about C. to about 150C. can be used. Generally, the lower the temperature, the longer the reaction will take to produce the product having the required molecular weight. Other factors which will affect the reaction temperature are, for example, the boiling point of the reactants or the reaction-exotherm. 1f the reaction is conducted at atmospheric pressure, it is conveniently done at temperatures below 30C. Since in most cases, the reaction produces heat, that is,

- it is exothermic, this exotherm will affect the overall temperature of the reaction, unless it is controlled.

Regarding reaction pressure, it is not critical. The reaction may be carried out at pressures below, at, or

above atmospheric. As pointed out above, a pressure 1n the following examples, methods of preparing the allyl halide/olefin products described above are given. All parts are by weight unless otherwise noted.

EXAMPLE 1 In a suitable vessel, a mixture of 11.5 (0.15 moles) parts allyl chloride and 75.6 (0.30 moles) parts octadecene-l was treated with 1 part AlCl in parts of n-propylchloride, at about 15C. Addition of the catalyst solution required 1 minute and the temperature of the system rose from 15C. to 26C. After 10 minutes, the reaction was stopped by adding approximately 35 parts of isopropanol. The product was washed three times, each time with about 50 parts of water. At the final wash, the aqueous phase was free of chloride. The organic solvent was stripped under vacuum at 170C. The yield of allyl chloride/octadecene reaction product was 6.9 parts. The molecular weight, determined by vapor pressure osmometry was 777. The product was a semi-solid yellow material and contained 3.62.percent chlorine.

EXAMPLE 2 The procedure of Example 1 was used except that 3.8 (0.05 moles) parts allyl chloride and 88.2 (0.35 moles) parts of octadecene-l were used. The yield was 36.3

parts of a semi-solid yellow material. The molecular weight was 916, via vapor phase osmometry.

EXAMPLE 3 The following general procedure was used to prepare a series of allyl chloride-octadecene reactant products. A saturated solution of AlCl in an alkyl chloride was added over a period of 2-4 minutes to the mixture of allyl chloride/octadecene-l in a suitable vessel. The reaction proceeded for 8-15 minutes. It was then shortstopped by adding about 100 parts of isopropanol. The reaction mixture was washed with 100 parts of H 0 and then again with 100-200 parts of a 1:1 H O/isopropanol solution. The washed organic layer was then stripped of solvent at 100l 75C. under vacuum. The product was obtained as an opaque. yellow material ranging in consistency from liquid-to semi-solid.

Following is a table indicating reactants, molar ratio. catalyst solvent, molecular weight of products obtained using the Example 3 procedure.

Table 1 Example AllylchloridezOctadecene-l AlCL, Product No. Molar Ratio Solvent M.W.

3A 1 :3 n-propylchloride 702 3B 1:4 n-propylchloride 794 3C 1:6 isopropylchloride 680 3D l :9 isopropylchloride 817 "By vapor phase osmomctry produced is the controlling factor, the reaction is allowed to proceed only until the required molecular weight as disclosed above is obtained. Times ranging from less than a minute to 24 hours can be used.

The reaction is generally short-stopped at the time when the reaction product has reached the desired molecular weight range. By short-stopped is meant that a substance is introduced into the reaction mixture to terminate the reaction. Suitable short-stop substances are materials having an active hydrogen such as alkanols. The type of short-stop material used is not critical.

As pointed out above, the allyl halide/olefin reaction products of this invention are emminently suited for improving the cold flow of fuel oils.

The fuels which are used in the compositions of this invention are petroleum hydrocarbons. They may be distillate fuels, residual fuels or blends of these two types. The distillate fuels are fractionation cuts from the distillation of either crude oil or the products from a cracking process. Cracked distillates are usually blended with straight run distillates before using. Kerosene is a typical distillate fuel. A residual fuel oil is the viscous product left after the more volatile fractions have been distilled or topped from the crude oil. It is the least expensive of the fuels obtainable from petrochamber of the cylinder; the cylinder is capped, inverted so that the fuel will not run into the other chamber, and placed in a bath set at the desired temperature for two hours. At the end of this time, the cylinder is leum. It is used alone aswell as in blends with the lower 5 inverted so that the cooled fuel now can run through boiling distillate fuel fractions. the capillary tube into the second chamber. The test These fuels are also characterized by their boiling apparatus is kept in the cooling bath while the fuel is point range. In general, the useful fuels have a boiling allowed to flow for 3 minutes. At this point, the amount i t a i f b t ()F t b t 1,(J()QF Th of fuel which has flowed through is measured. It is reboiling point of most commonly used fuels ranging 1O Ported as F Cent recovery of total fuel Sample usedfrom about 200F. to about 800F. Useful fuels include The higher the P cent of fuel which passes through, di l f l n grade DEA, D121], 112; domestic f l the better cold flow the fuel composition has. Thus, for il N 1 2 3 4 d 5; j fu l Such as 4 112.4 example if ml. of fuel oil flows from the first champ-5 and the likfi ber to the second chamber, the Enjay Fluidity Recov- The improved fuel oil compositions are prepared by 15 50 P dissolving the allyl halide/olefin reaction products di- Following is a table of Enjay Fluidity results obtained rectly in the fuel. No special equipment is required and for a series of fuel oil compositions of this invention.

Table 2 ENJAY FLUlDlTY Concentration Fuel" Additive Prepared" From Catalyst of Additive Molecular Weight" Recovery No. Allyl Halide (Moles) :Olefin (Moles) Used (Wgt. 7(1) of Additive 1 Allyl chloride None AICI (1.1% 358 5 2 None Octadecenc-l AlCl 0.1% 848 2.5 3 None Tetradecenc-l AlCl (1.1% 582 U 4 Allyl chloride( l Octadecene-l( 1 AlCl 0.05% 728 5 Allyl chloride( l Octadcccne-l(2) AlCl (1.1% 777 75 6 Allyl chloride( 1 Octadecene-1(3) AlCl (1.1% 702 100 7 Allyl chloride(l Octadecenc-l(4) AlCL, 0.1% 794 100 8 Allyl chloride( 1) Octadecene-1(4) AlCl 0.05% 794 97.5 9 Allyl chloride( l Octadecene-l(4) AlBr 0.1% 691 95 1(1 Allyl chloride( 1 Octadecene-l(5) AlCl 0.1% 1025 95 l 1 Allyl chloride( 1 Octadecene-1(6) AlCL, 0.1% 680 100 12 Allyl chloride( 1) Ocladecene-l(7) AlCl 0.1% 916 90 13 Allyl chloride( 1) Octadecene-l( l) AlCl; 0.1% 817 12.5 14 Allyl chloride( 1) Tetradecene-l(3) AICL, 0.1% 805 25 15 Allyl chloride( 1 Tetradecene-l/ hexadecenc-l(4)" AlBr 0.1% 680 2O 16 Allyl chloride(l) Octadecene-l( l) AlCl 0.1% 737 100 l7 Allyl chloride(4) Octadeccne-1( l) AlCl 0.1% 576 25 "The base fuel was a commercial No. 2 grade fuel oil Using procedures as described herein By vapor phase osmometry "2 parts by weight C ll pan by weight C conventional liquid mixing or blending equipment may be used. The cold flow improving additive on the other hand can be dissolved in a suitable solvent such as toluene, xylene, isopropanol, kerosene, or fuel oil in order to form an additive concentrate. This additive concentrate could then be used to prepare the additive fuel oil compositions. Additive concentrates can contain up toper cent by weight of the allyl halide/olefin reaction product.

In order to show the unobvious improvement in cold flow in fuel compositions of this invention, the fuel oil compositions were evaluated using the Enjay Fluidity Test. The Enjay Fluidity Test measures the flow characteristics of fuel oils through a narrow orifice. The procedure and test equipment are fully described in Enjays brochure ELD-48439. The contents of that brochure are incorporated by reference as part of this specification. Briefly, the test involves measuring the amount of fuel oil which flows through an orifice in a given time at a given temperature. The testing device consists of a two-compartment cylinder connected by means of a capillary tube one-half inch long and 2.25 mm inside diameter. Each chamber is calibrated. Forty milliliters of the fuel oil to be tested are placed in one The data in Table 2 demonstrates the effectiveness of the allyl halide/olefin additives as cold flow improvers. The data for Fuels l, 2, and 3 show that low molecular weight reaction products of either allyl chloride alone or a C or C olefin alone do not effect any significant cold flow improvement in fuel oil. When the additive used is a low molecular weight reaction product of allyl chloride and a C to C olefin, the cold flow of the fuel oil is significantly improved (Fuels 4-l7). Fuels 6-12 show a recovery of almost percent in each case. Since this high recovery data indicates greater effectiveness, the additives prepared from allyl ch1oride:octadecene-l in a molar reaction ratio of from about 1:3 to about 1:8 are more effective and are therefore preferred. However, it is evident that all the allyl halide- :olefin reaction products prepared as herein described are effective cold flow improvers for fuel oil.

The fuel oil compositions of this invention may contain other additives provided that these additives do not adversely effect the cold flow improving properties of the presently claimed additives. Such other additives include cetane improvers such as amyl nitrate and the like; dispersants such as the alkenyl succinic anhydride derivatives and the like; corrosion inhibitors such as linoleic acid dimers, sorhitan monoleutc and the like;

smoke reducers such as alkaline earth sulfonates, (methylcyclopentadienyl) manganese tricarbonyl and the like; dyes and other commonly used additives.

Having fully described the additives and fuel compositions of the present invention, it is intended that the invention be limited only within the spirit and scope of the following claims.

I claim:

1. The product obtained from the process which comprises reacting allyl halide with monoolefin having from 14 to about 18 carbon atoms, in the presence of a catalytic quantity of an aluminum halide selected from aluminum chloride and aluminum bromide, said aluminum halide being dissolved in C C alkyl halide, said allyl halidezolefin molar ratio being from 1:3'to about 1:8, at temperatures from about 0C. to below 30C. and at atmospheric pressure, said product having a molecular weight of from about 550 to about 1,200.

num halide selected from aluminum chloride and aluminum bromide, said aluminum halide being dissolved in C -C alkyl halide, said allyl halidezmonoolcfin molar ratio being from about 1:3 to about 1:8, at temperatures from about 0C. to below 30C. and at atmospheric pressure, said product having a molecular weight of from about 550 to about 1,200. 

2. The product of claim 1 wherein said monoolefin is octadecene-1 and said allyl halide is allyl chloride.
 3. The product obtained from the process which comprises reacting an allyl halide with a mixture of monoolefin having from 12 to about 20 carbon atoms, in which those having 18 carbon atoms are predominant, in the presence of a catalytic quantity of an aluminum halide selected from aluminum chloride and aluminum bromide, said aluminum halide being dissolved in C2-C5 alkyl halide, said allyl halide:monoolefin molar ratio being from about 1:3 to about 1:8, at temperatures from about 0*C. to below 30*C. and at atmospheric pressure, said product having a molecular weight of from about 550 to about 1,200. 